Triazole azo pigments

ABSTRACT

Azo pigments of the formula WHEREIN R1 denotes an aromatic radical, R4 denotes a cyclic radical of aromatic character, R2 denotes a naphthalene radical in which the azo, hydroxyl and -CO group are in the 1,2,3position, R3 denotes an arylene radical and R5 denotes an alkyl or aryl group or a hydrogen atom, are useful for coloring plastics and lacquers in orange ro red shades of excellent fastness properties.

United States Patent [1 1 Roueche 1 Feb. 27, 1973 [5 1 TRIAZOLE AZOPIGMENTS 2,838,486 6/1958 Mueller et al. ..260/157 [75] Inventor: ArmandRoueche, Bottmingen, Swit- Zefland Primary Exammer-Floyd D. H1gelAttorney-Harry Goldsmith, Joseph G. Kolodny and [7 3] Assignee:Ciba-Geigy AG, Basel, Switzerland Mario Monaco [22] Filed: April 22,1970 [57] ABSTRACT [21] Appl. No.: 30,980

Azo pigments of the formula [30] Foreign Application Priority Data May7, 1969 Switzerland ..7010/69 7 fij R -N=N-Rz-CONHR -o 52 US. Cl...260/157, 106/22, 106/23, a R

106/228 Q, 117/123, 117/138.8 R, 117/138.8B, 117/138.8 D, l17/138.8 E,R5 117/138.8 F, 260/140, 260/203, 260/204, 260/308 R [51] Int.Cl.....C09b 29/36, C091) 33/12, C09b 43/14 wherein R denotes an aromaticradical, R denotes a [58] Field of Search ..260/157, 146 cyclic radicalof aromatic character, R denotes a naphthalene radical in which the azo,hydroxyl and [56] References Cited -CO group are in the 1,2,3-position,R denotes an arylene radical and R denotes an alkyl or aryl group UNITEDSTATES PATENTS or a hydrogen atom, are useful for coloring plastics2,848,447 8/1958 Kracker et al ..260/157 and lacquers in orange r0 redshades of excellent fast- 2,872,441 2/1959 Kracker et a] ..260/157 nessproperties. 3,124,565 3/1964 Schilling et al. ..260/ 157 3,498,9663/1970 Mueller ..260/157 8 Claims, N0 Drawings TRIAZOLE AZO PIGMENTSThis invention is based on the observation that new valuable azopigments of the formula wherein R denotes an aromatic radical, R,denotes a cyclic radical of aromatic character, R denotes a naphthaleneradical in which the azo, hydroxyl and CO groups are in the1,2,3-position, R denotes an arylene radical and R denotes an alkyl oraryl group or preferably a hydrogen atom, may be obtained a) bycondensing a carboxylic acid halide of the formula I lt,-N=N-lu-oonulwith an amine of the formula or b) a diazo or diazoamino compound of anaromatic amine is coupled with a coupling component of the formula Sincethe products according to the invention are pigments, they do notcontain groups which confer solubility in water, especially acid groupswhich confer solubility in water, for example sulphonic acid groups orcarboxylic acid groups.

The carboxylic acids on which the halides required for embodiment (a) ofthe process according to the invention are based may be obtained bycoupling a diazo compound of a carbocyclic or heterocyclic aromaticamine, especially an aminobenzene, with a 2,3-hydroxynaphthoic acid ofthe formula 5 firm wherein Z denotes a hydrogen or halogen atom, or anitro, cyano or alkoxy group.

Diazo components of particular interest are those of the formula whereinX, denotes a hydrogen or halogen atom or an alkyl group, X and X eachdenotes a hydrogen or a halogen atom, an alkyl, alkoxy, phenoxy, nitro,cyano,

carboxylic acid ester, alkylsulphonyl, aralkylsulphonyl,trifluoromethyl, sulphonic acid amine or sulphonic acid ester group or agroup of the formula CONHR, in which R denotes a hydrogen atom, an alkylgroup or a phenyl group which may be substituted, for example by halogenatoms or alkyl, trifluoromethyl, alkoxy, nitro, cyano, carbalkoxy oralkanoylamino groups.

As examples of diazo components, the following amino-benzenes may bementioned: 2-, 3- or 4- chloroaniline, 3,4-di-chloroaniline, 2,3-dichloroaniline, 2,4-dichloroaniline, 2,5- dichloroaniline,2,6-dichloroaniline, 2,4,5-

trichloroaniline, 2,4,6-trichloroaniline, 2-, 3- or 4- bromoaniline,2,4-dibromoaniline, 2,5-dibromoaniline, Z-methyl-S-chloroaniline,2-methyl-4-chloroaniline, 2- methyl-3-chloroaniline, 2-chloro-5-trifluoromethylaniline, 2-, 3- or 4-nitroaniline, 4-chloro-2-nitroaniline, 2-chloro-4-nitroaniline, 2-nitro-4-trifluoro-methylaniline, 4-nitro2- trifluoromethylaniline, 3 ,5-di-(trifluoromethyl aniline, 3-trifluoromethylaniline, 4-methyl-3-nitroaniline, 2,4-dimethyl-3-nitroaniline, 2-methyl-5- nitro-aniline,2-methyl-4-nitroaniline, 2- and 4-methoxyaniline,2-methoxy-4-nitroaniline, 3-chloro-4-methoxyaniline,Z-methoxy-S-nitroaniline, 2-methoxy-5- chloroaniline,2-methoxy-5-trifluoromethylaniline, 2-amino-4-trifluoromethyl-4-chlorodiphenylether, 2- nitro-4-ethoxyaniline,2-amino-4-chlorodiphenylether,

2-arnino-2', 4-dichlorodiphenylether, 2-amino-4,4'-dichlorodiphenylether, 1-amino-2-carboxylic acid methyl ester,l-amino-2-chloro-5-carboxylic acid methyl ester,1-amino-2-chloro-5-carboxylic acid phenyl ester, 2-amino-5-nitrobenzoicacid methyl ester, 4-amino-3-nitro-benzotrifluoride, 2-amino-5-nitrobenzotrifluoride, l-amino-2-methylbenzene-5- carboxylic acid methylester, l-amino-2-methylbenzene-S-carboxylic acid phenyl ester,l-amino-Z- chlorobenzene-S-carboxylic acid methylamide, 2-amino-4-tri-fluoromethyldiphenylether, 4-methyl-3- aminobenzoic acidamide, 4-chloro-3-aminobenzoic acid amide, 2,4-dichloro-5-aminobenzoicacid amide, 4-methoxy-3-aminobenzoic acid amide, 4-methyl-3-aminobenzoic acid 2-chloro-5'-trifluoromethyl-anilide,4-chloro-3-aminobenzoic acid 2',5'-dichloroanilide,4-chloro-3-aminobenzoic acid 2'-chloro-5-carbomethoxyanilide,4-chloro-3-aminobenzoic acid 3'- chloroanilide, 4-chloro-3-amino-benzoicacid 2'- chloro-S-trifluoromethylanilide, 4-chloro-3- aminobenzoic acid3-trifluoromethylanilide, 4-chloro- 3-aminobenzoic acid3',5-bis-(trifluoromethyl)-anilide, 4-chloro-3-aminobenzoic acid 2,4',5-trichloroanilide, 2,4-dichloro-5-aminobenzoic acid2',5'2,4-dichloro-S-amino-benzoic acid 2,4'-dichloroanilide,2,4-dichloro-5-aminobenzoic acid 3'-trifluoromethylanilide,2,4-dichloro-5- aminobenzoic acid 3-chloroanilide, 5-amino-4-methoxy-Z-chlorobenzoic acid 3'-trifluoromethylanilide,4-methyl-3-aminobenzoic acid 2',5-dichloroanilide,4-methyl-3-aminobenzoic acid 3-trifluoromethylanilide,4-methoxy-3-aminob enzoic acid 3'- chloroanilide,4-methoxy-3-aminobenzoic acid 2',5'- dichloroanilide,4-methoxy-3-aminobenzoic acid 2,4, S'-trichloroanilide,4-carbomethoxy-S-aminobenzoic aminobenzoic acid2'-chloro-5'-trifluoromethylanilide,

4-methoxy-3-aminobenzoic acid 2,5'-dimethoxy-4'- chloroanilide,4-methoxy-3-aminobenzoic acid 2',5- dimethyl-4" -chloroanilide,4-aminobenzoic acid 2,4- dichlorophenylamide, 4-amino-benzoic acid2'-chloro- 5 '-trifluoromethylphenylamide, 4-amino-3-methylbenzoic acid3-trifluoromethylphenylamide, 4-amino- 3-methylbenzoic acid4'-chlorophenylamide, 4-amino- 3-nitrobenzoic acid2',5'-dichlorophenylamide, 4- amino-3-methylbenzoic acid methyl ester,4-amino-3- methylbenzoic acid phenyl ester, 4-methoxy-3- aminobenzoicacid phenyl ester and 4-methyl-3- aminobenzoic acid p-chlorophenylester.

The resulting azo dyestuff carboxylic acids are treated with agentswhich are capable of converting carboxylic acids into their acidhalides, for example acid chlorides or bromides, especially withphosphorus halides, for example phosphorus pentabromide or phosphoruspentachloride to trichloride, phosphorus oxyhalides and preferably withthionyl chloride.

The treatment with such acid-halogenating agents is advantageouslycarried out in inert organic solvents, for example dimethylformamide,chlorobenzenes, for example mono-chlorobenzene or dichlorobenzene,toluene, xylene or nitro-benzene; the five last-mentioned compounds maybe used together with diinethylformamide. When manufacturing thecarboxylic acid halides it is as a rule desirable first to dry the azocompounds made in an aqueous medium or to free them from water byazeotropic distillation in an organic solvent. This azeotropic dryingcan, if desired, be carried out immediately prior to the treatment withthe acidhalogenating agents.

The resulting azo dyestuff carboxylic acid chlorides are condensed withamines of formula (3), preferably with a monoamine of the formula andespecially with a monoamine of the formula The azo dyestuff carboxylicacid chlorides can also be condensed in a molar ratio of 2:1 withdiamines of the formula especially with those of the formula triazole,4-amino-4"-chloro-2,5-diphenyl-1 ,3,4- triazole,4'-amino-4"-methoxy-2,5-diphenyl-l ,3 ,4- triazole,4'-amino-3"-methyl-2,5-diphenyl-l ,3,4- triazole, 4 '-amino.-4''-carbomethoxy-2,S-diphenyl- 1,3,4-triazole, 3'-amino-6'-chloro-2,5-diphenyll ,3,4- triazole,2-(4'-aminophenyl)-5-(2"-furyl)-l ,3,4-triazole,2-(4'-aminophenyl)-5-a-naphthyl-l ,3 ,4-triazole, 4' ,4'A-diamino-2,5-diphenyll ,3 ,4-triazole, 4,4 diamino-3,3"-dimethyl-2,5-diphenyl-l,3,4-triazole, 4',4' 'A-diamino-3 '-methyl-2,5-diphenyl-l3 4-triazole, 4-(p-aminophenyl)-2,5-diphenyl-l ,3,4-triazole, and 44"A-bis-(p-aminophenyl)-2,5-diphenyl-l ,3,4-triazole.

The condensation of the aforesaid carboxylic acid halides and the aminesis preferably carried out in an anhydrous medium. Under these conditionsit generally takes place surprisingly easily at temperatures within theboiling range of the common organic solvents for example toluene,monochlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene andthe like. In order to accelerate the reaction it is generally advisableto use an acid-binding agent, for example anhydrous sodium acetate orpyridine. The resulting dyestuffs are in part crystalline and in partamorphous and are in most cases obtained in very good yield and in thepure state. It is advisable first to separate the acid chloridesobtained from the carboxylic acids. In some cases, however, theseparation of the acid chlorides can be dispensed with without harm, andthe condensation carried out immediately following the manufacture ofthe carboxylic acid chlorides.

According to the embodiment b) of the process according to the inventionthe new dyestuffs may be obtained by diazotizing an aromatic amine,preferably an aminobenzene, especially one of formula (6), and couplingwith a coupling component of formula (4).

The coupling components can be obtained by condensation of a2,3-hydroxynaphthoic acid chloride with an amine of formula (3),especially an amine of formula (7).

The coupling takes place by gradual addition of an aqueous alkalinesolution of the coupling component to an acid solution of the diazoniumsalt. The coupling is advantageously carried out at a pH value of 4 to6. The pH value is advantageously adjusted by adding a buffer. Suitablebuffers are for example the salts, especially the alkali metal salts, offormic acid, phosphoric acid or especially acetic acid. The alkalinesolution of the coupling component advantageously contains a wettingagent, dispersing agent or emulsifier, for example an aralkylsulphonate, for example dodecylbenzene sulphonate or the sodium salt of1,1 '-naphthylmethane sulphonic acid, polycondensation products ofalkylene oxides, for example the product of the action of ethylene oxideon p-tert.-octylphenol, and also alkyl esters of sulphoricinoleates, forexample n-butyl sulphoricinoleate. The dispersion of the couplingcomponent can also advantageously contain protective colloids, forexample methylcellulose, or minor amounts of inert organic solventswhich are sparingly soluble or insoluble in water, for exampleoptionally halogenated or nitrated aromatic hydrocarbons, for examplebenzene, toluene, xylene, chlorobenzene, dichlorobenzene ornitrobenzene, as well as aliphatic halogenated hydrocarbons, for examplecarbon tetrachloride or trichloroethylene, and also organic solventswhich are miscible with water, for example acetone, methyl ethyl ketone,methanol, ethanol or isopropanol.

The coupling can also be advantageously carried out by continuouslyadding an acid solution of the diazonium salt to an alkaline solution ofthe coupling component in a mixing nozzle, whereby immediate coupling ofthe components takes place. The resulting dyestuff dispersion iscontinuously withdrawn from the mixing nozzle and the pigment isseparated by filtration.

The aryldiazoamino compounds to be used according to embodiment b) ofthe process according to the invention may be obtained according toknown methods by coupling an aryldiazonium salt with a primary amine orpreferably with a secondary amine. The most diverse amines are suitablefor this purpose, for example aliphatic amines, for example methylamine,ethylamine, ethanolamine, propylamine, butylamine, hexylamine andespecially dimethylamine, diethylamine, diethanolamine,methylethanolamine, dipropylamine or dibutylamine, aminoacetic acid,methylaminoacetic acid, butylaminoacetic acid, aminoethane sulphonicacid, methylaminoethane sulphonic acid, guanylethane sulphonic acid, [3-aminoethylsulphuric acid; alicyclic amines, for example cyclohexylamine,N-methylcyclohexylamine and dicyclohexylamine; aromatic amines, forexample 4- aminobenzoic v acid, sulphanilic acid, 4-sulpho-4-aminobenzoic acid, (4-sulphophenyl)-guanidine, 4-N- methylamino benzoicacid, 4-ethylamino benzoic acid, l-aminonaphthalene-4-sulphonic acid and1- aminonaphtha1ene-2,4-disulphonic acid; heterocyclic amines forexample piperidine, morpholine, pyrrolidine and dihydroindole, andfinally also sodium cyanamide or dicyandiamide.

As a rule, the resulting diazoamino compounds are sparingly soluble incold water and can be separated from the reaction medium in acrystalline form, if desired, after salting out. In many cases the moistpress cakes can be used for further reactions. In individual cases it isadvantageous to dehydrate the diazoamino compounds by vacuum dryingprior to the reaction.

The coupling of the diazoamino compound with the coupling componenttakes place in an organic solvent, for example chlorobenzene,o-dichlorobenzene,

nitrobenzene, pyridine, ethylene glycol, ethylene glycol monoethyl etheror mono-methyl ether, dimethylformamide, formic acid or acetic acid.When using solvents which are miscible with water it is not necessary touse the diazoamino compounds in an anhydrous form, for example thefilter cakes which are moist with water may be used.

The coupling is advantageously carried out under warm conditions,preferably at temperatures between to 180 C., in an acid medium and ingeneral takes place very rapidly and completely. When neutral solventsare used, the addition of and acid, for example hydrochloric acid,sulphuric acid, formic acid or acetic acid is of advantage. As aresultof their insolubility, the resulting pigments can be isolated from thereaction mixture by filtration. An after-treatment with organicsolvents, as is necessary with pigments obtained by aqueous coupling, istherefore not necessary in most cases.

The new dyestuffs are valuable pigments which can be used in a finelydivided form for pigmenting high molecular organic material, for examplecellulose ethers and cellulose esters, polyamides or polyurethanes orpolyesters, acetylcellulose, nitrocellulose, natural or syntheticresins, for example polymerization resins or condensation resins, forexample aminoplasts, especially urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefines,for example polyethylene, polypropylene, polystyrene, polyvinylchloride, polyacry'lonitrile, polyacrylic acid esters, rubber, casein,silicone and silicone resins, individually or as mixtures. It isimmaterial whether the high molecular compounds mentioned are in theform of plastic masses, melts or spinning solutions, lacquers orprinting inks. Depending on the end use, it is advantageous to use thenew pigments as toners or in the form of preparations. I

The new pigments are distinguished by excellent fastness properties,especially fastness to light and migration. The good fastness tomigration of the new azo pigments is surprising since they contain onlyone carboxylic acid group and according to Fuchs, supplement to Chimica1968, page 159, at least two carboxylic acid amide groups are requiredto ensure good fastness to migration of an azo pigment.

in the examples which follow the parts denote parts by weight and thepercentages denote percentages by weight, unless otherwise stated.

EXAMPLE 1 36.5 Parts of the dyestuff obtained by coupling diazotized2,5-dichloroaniline with 2,3-hydroxynaphthoic acid are heated for 2hours at to C. with 390 parts of o-dichloro-benzene, 16.5 parts ofthionyl chloride and 2 parts of dimethyl-formamide whilst stirring,whereby all the material dissolves. After the reaction mixture hascooled, the uniformly crystalline azo dyestuff monocarboxylic acidchloride is isolated by filtration and washed with 400 parts of benzeneand then with 200parts of petroleum ether. After drying at 50 C. invacuo, 29.5 parts of a red crystal powder are obtained.

9.2 Parts of the azo dyestuff monocarboxylic acid chloride .thusobtained are stirred with 500 parts of dichlorobenzene and heated to 80to 90 C. A warm solution of 5.8 parts of 4'-amino-2,5-diphenyl-l,3,4-triazole in 20 parts of dimethyl-formamide and 20 parts ofo-dichlorobenzene is then added and the mixture is heated to 140 to 145C. for 12 hours. The sparingly soluble pigment which precipitates in afinely crystalline form is filtered hot, washed with hoto-dichlorobenzene until the filtrate issues clear, then with coldmethanol and finally with hot water. After drying at 80 C. in vacuo, 9.9parts of a soft-grained powder are obtained, the powder beingpractically insoluble in the customary solvents. It dyes polyvinylchloride films as well as lacquers red shades of excellent fastness tolight, migration and overstripe bleeding.

The pigment corresponds to the formula 7 EXAMPLE 2 47.5 Parts of thedyestuff obtained by diazotizing 2,4,S-trichloroaniline with glacialacetic acid, hydrochloric acid and sodium nitrite and coupling with2,3-hydroxynaphthoic acid, are mixed with 650 parts ofo-dichlorobenzene, 20 parts of thionyl chloride and 2 parts ofdimethylformamide and heated for two hours at 135 to 145 C. whilestirring whereby all the material dissolves. When the reaction mixturehas cooled, the uniformly crystalline monocarboxylic acid chloride ofthe dyestufi is isolated by filtration and washed with 400 parts ofbenzene and then with 200 parts of petroleum ether. After drying at 50to 60 C. in vacuo, 39 parts of the dyestuff acid chloride are obtainedas a red crystalline powder.

1.25 Parts of this acid chloride are stirred with 40 parts ofo-dichlorobenzene and heated to 100 C. A warm solution of 0.8 part of4-amino-4"-methyl-2,5 diphenyl-l,3,4-triazole in 100 parts ofodichlorobenzene is then added and the mixture heated to 140 to 145 C.for 12 hours. Thereafter the finely crystalline, sparingly soluble,pigment is filtered hot, washed with hot o-dichlorobenzene until thefiltrate issues clear, then with cold methanol and finally with hotwater. After drying at 80 to 85 C in vacuo, 1.4 parts of a soft powderare obtained which is practically insoluble in the customary solventsand which dyes polyvinyl chloride films as well as lacquers red shadeshaving excellent fastness to light, migration and overstripe bleedmg.

"EXAM'P'LE 3 27.5 Parts of the dyestuff obtained by diazotizing 4-chloro-3-aminobenzoic acid (2'-chloro-5 trifluoromethyl)-phenylamidewith glacial acetic acid, hydrochloric acid and sodium nitrite andcoupling with 2,3-hydroxynaphthoic acid, are mixed with 600 parts ofchlorobenzene, 115 parts of thionyl chloride and 3.5 parts ofdimethylformamide and heated for 10 hours at to C. whilst stirring. Whenthe reaction mixture has cooled, the uniformly crystallinemonocarboxylic acid chloride of the dyestuff is isolated by filtration,washed with cold benzene and dried at 50 C. in vacuo.

1.7 Parts of this acid chloride are stirred with l30 parts ofo-dichlorobenzene and heated to 60 C. A warm solution of 0.75 part of4'-amino-2,5-diphenyl- 1,3,4-triazole in 4 parts of dimethylformamide isthen added and the mixture heated at 140 to 145 C. for 12 hours.Thereafter the crystalline, sparingly soluble pigment is filtered hot,washed with hot 0- dichlorobenzene, cold methanol and hot water, anddried in vacuo at to C. The resulting dyestuff of the formula N- ll is ared pigment which is sparingly soluble to insoluble in the customarysolvents and which dyes polyvinyl chloride films as well as lacquersexcellent red shades which are fast to light, migration and overstripebleedmg.

The Table which follows gives further components from which monoazopigments can be obtained in accordance with the process described inparagraph 1, when 1 mol of a diazo compound of the amines named incolumn is coupled with 1 mol of the 2,3-hydroxynaphthoic acid named incolumn II, the resulting monoazo dyestuff carboxylic acid is convertedinto the acid chloride and condensed with 1 mol of the amine named incolumn III. Column IV indicates the color of a polyvinyl chloride filmdyed with the resulting pig- The pigment corresponds to the formulament.

1 ll III IV 1 2,5-dlclmur m|ilIi|w .3,B-hydmxynaphthoicleunlno-W-mothyl-2,fi-dipllenyl-Lii,-l- Rod.

m-ld. lriuzolu. .5 ..(l0 do -t-mnln0-3,4- limuthyl-2,5-dlpln'nyl-l,3,4-Brown.

trlnzolo. 3 "do fi-nitro-Z,3-liydroxy- (l0 Rml-ornntw.

nnphtlmli: ncld. l do (Lhromo-Z,3hydroxyilo Red.

mmhtlmlu acid. 6 do... (lo 4-amino-2,fi-dlplmnyl-l,3,4-trinzolo Roll. 0do (i-nwthoxy-J,li-hyrlroxy- (lo Claret. lmphtholu llCltl. 7 .(l0......(l0 -l-mnlnot"-motl1yl-2,54lipl1cnyll,3,4- Do.

trlnzolo. t4 410.. 4'-nmluo-3-motllyl-2, 5-dlpl10nyl'1, 3, 4- Orange.

.. 2,3-hydroxynaphthoic :icld.

triazolo.

-. -ld s t nys I II III IV do 4'-arxinim1)-2"chi0ro-2,5-diphenyl-L3, 4-Brown.

t azo e. 2-methoxy-4-nitroanilina dc 4amino-4"-methyi-2,5-diphenyl-1,3,+ Claret.

triazole. 11 d0 4'-amino-2, 'dipheny1-1, 3, 4-triazole Scarlet. 22,4,5-trichl roaml 4-amino-3-methyl'2,5-diphenyl-1,3,4- Red.

triazole. 13 Z-chloro-5-t1iflu0romethy1aniline do4'-amino-2,5-diphenyl-1,3,4-t1iazole Red- 14 .do d04'-amin(114-methy1-2,5-dipheny1-l,3,4- Brown.

triazo e. 15 3-amino-4-chlorobenzoic acid 2'-mathy1-3- do4'-amino-2,5-dipheny1-1,3,4-trlazole Orange.

chiorophenylamide. 6 3-amin0-4-ehlorobenzoic acid 3-carbomethd0 do D0.

oxyphenylamide. 17 ,do d 4-amino-4"-methyl-2, fi-diphenyl-l, 3,

triazole. 18. 3-amino-4-chlorobenzoic acid 3-trifluoroundo d D0-methylphenylamide. 19 3-amino-4-chlorobenzoic acid 2ch1oro-5- do3"amino-6-chlor0-2,5-t1lD y -L tniiuoromethylphenylamide. triazole. 23-am1no-4-chlorobenzoic acid methyl ester d0 4'-amin0-4"methyi-2,5dipheny1-1,3,4- Browntriazole. 21 3-a nlno-4-chloropenzoicacid pheny1amlde d 4- mi -2,5diphenyl-1,3,4-trlazole Scarlet. 22..Z-mtro-ehloramline d 4'. i -4"-chl r -2,5-diphenyl-i,3,4-triazole.Brown. 23.. 2,5-d1ch10raniline d Red. 2,4,5-trichloroaniline d Red. 25..2-ch1oro-5-trifluoromethylaniline do Red-orange. 262-methoxy-5-chloroani1ine d d Bluigh-tinged 27 2-methoxy-4-nitroaniiinedo; do 28.. 2-nitro-4-tri.fluoromethylaniline do 29.-2,5-dichloroaniline 6-methoxy-2,3-hydroxynaphthoic acid. 30..2-benzylsulphone-5-tnfiuoromethylaniline 2,3-hgdroxynaphthoic Orange aci31 4-chloro-3-aminobenzoic acid 3'-trifluoro- .do .do Red-orange.

methyl-anilide. Hhloro-li'aminobenzoic acid 2-choioro-5- .do4-amino-3-methyl-4"-chloro-2,5-diphenyl Do.

trifluoromethylanilide. 1,3 -triazole. 2,5-dichloroaniline do "do Brown.2,4,5-trich1oroaniline do -do 2-chloro-5-carbomethoxyanilin do do. eAnthranilic acid methyl ester do d0 Red. 37--... 2,5-dichloroaniline do4amino-4-methoxy-2,5-diphenyl-l,3,4- Red.

triazo e. 38 ..do 6-bromo-2,3-hydroxydo Rednaphthoic acid. 392,4,5-tnchloroanilme. 2,3-hiyldroxynaphtholc do Red.

ac 40 2-ch1oro-fi-trifiuoromethylaniline do do Red. 412,4,5-trichloroaniline do 4'-amino-2,4-dichloro-2,5-diphenyl-l,3,4-Brown.

triazole. 42 2-benzyisulphone-5-trifiuoromethylani1ine do o Orange.43-.. 2,5-dlchloroaniline do 4-amino-3methyl-2,4"-diehloro-2,5- Brown.

diphenyl-1,3,4-triazole. 44 2,4,5-trichloroaniline ..do do D0. 452,5-dich1oroaniline ..do 4-amino-2,5"dichl0ro-2,5diphenyl- D0.

1,3,4-triazole. 46 Anthranilieacidmethylester .do .do Orange. 472,5-dichloroaniline ..do 2-(4i-amlinophenyl)-5-(2-furyl)-1,3,4- Red.

tr 2.10 e. 48 4-chloro-3-aminobenzcic acid 3-triflu0ro- .d0 "do Red-orag methylanilide. 49 2,4,5-trich1oroaniline do2'(4'-amlinophenyl)-5-a-naphthyl-1,3,4- Red.

- triazo e. 50. 2-benzyisulphone-5-trifiuoromcthylaniline ..do .doOrange- 51. Anthranilic acid methyl ester do4-amino-4-carbomethoxy-2,5-dipheny1- Scarlet.

1,3,4-triazole. 52. 2,4,5-trichioroaniline do d0 Red. 53.2,5-dichloroaniline "do... do Red. 54 a-ethoxy-tl-aminobenzoic acid3"trifiuorodo 4'-amin04"-chl0ro-2,5-d1phenyl'1,3,4- Bluishmethylanilide.triazole. tinged red. 55 4-methyl-3'aminobenzoic acid ethyl ester do .doRed. 56 2,5-dichloroani1ine 6- 'tro-2,3hydroxy- .do Red.

' naphthoic acid. 57 2-ethylsull'one-5-trifiuoromethylanil.ine 2,3hydroxynaphthaloic ..do Orange.

2191 58 3-amino-4-chlorobenzoic acid (4-chloro) .....do ..do Red.

phenylester. 59 3-amino-4-ch1orobenzenesulfonic acid-2,5'- do ..do Red.

dichlorophenylester. 60 3-amino-4-methylbenzenesuifonic acid-8- do doRed.

trifiuoromethylphenylamide. 61 3-amino-5-chlorobenzoic acid amide do4???in0-4carbonicthoxy-2,5-diphenyl- Red.

, ,-triazo e. 62 2-mcthoxy-4-chloroaniline d o4'-amino-4-chioro-2,5-diphenyl-1,3,4- Red with triazole. bluish tinge.63 4*chlggg-3-aminobenzoic acid 2-methoxy- ..do "do Red.

am e. 64 4-chloro-3-amlnobenzoic acid methylamid do d0. Red. 65.-4-phenoxy3-amino-benzotrifluoride do. Red 66 3-amino-4-chiorobenzoicacid phenyiester. do do Red. 67 4-chloro-3-aminobenzoic acid 3- do-amin0-4"-trifluoromethyl-2,5-diphcnyl- Red.

trifiuorumethylanilide. 1,3,4-triazolc.

EXAMPLE 4 of o-dichlorobenzene 15 then added and the mixture 15 heatedto 140 to 145 C. for 12 hours. Thereafter the 3.9 Parts of the dyestuffacid chloride described in finely crystalline, sparingly soluble pigmentis filtered Example 1 are stirred with 180 parts of o- .hot, washed withhot o-dichlorobenzene until the fildichlorobenzene and heated to to C. Ahot soluti-ate emerges colorless, then with cold methanol and tion of1.25 parts of 4',4"-diamino-2,5diphenyl-l,3,4- finally with hot water.After drying at 80 to 85 C. in triazole in 8 parts of dimethylformamideand 10 parts vacuo, 3.2 parts of a soft powder are obtained which ispractically insoluble in the customary solvents and is obtained in goodyield. The properties of the pigment which dyes polyvinyl chloride filmsas well as lacquers can be improved by after-treatment in an organicsolexcellent brown shades which are fast to light, migravent, forexample nitrobenzene. The pigment is tion and overstripe bleeding.sparingly soluble to insoluble in the customary solvents The pigmentcorresponds to the formula and dyes polyvinyl chloride film and lacquersred- I 01 N i l The Table which follows gives further components orangeshades of good fastness to migration overstripe from which disazopigments can be obtained in acbleeding and light. cordance with theprocess described in paragraph 1, EXAMPLE6 when a diazo compound of theamine named in column I is coupled with the 2'3 hydmxynaphthoic acids2.0 Parts of the diazoamlno compound of the formula named in column II,the resulting monoazo dyestuff s oioznt carboxylic acid is convertedinto the acid chloride and 1r 2 mols thereof are condensed with 1 mol ofthe dlamlne N N N named in column 111. Column IV indicates the color ofa polyvinyl chloride film dyed with the resulting pigment. F,

I 11 Ill 1V 1 2,5 dichloroanilanu 2,34liplroxynuphtlmlu 4,4limnino-l,2,5-tripl|unyl-l,3,4-Lriuzolu Rod.

11C 2 2,4,fi-trichloroanilinc do4,4"-(llullllll0-2,5-(l1])ll0llyl-l,3,4-l/l'l:lZ()l0 Brown. 32-chloro-5-trifluoromctllyluiiiliuc lo d0 Rod. 42-nitro-4-trifiuoromcthylauiliue du do Brown. 5 ..tl0 (lo4,4-diamino-3,3"-di1ncthyI-2,5- Do.

dipheuy1-1,3,4-triazole.

EXAMPLE 5 manufactured by coupling diazotized3-amino-4-ethylsulphonyl-benzotrifluoride with morpholine in an alkalinemedium, and 2.1 parts of 4'-(2"-hydroxy-3'-naphthoyl)-amino-4"-methyl-2,5-diphenyl-1,3,4- triazole are suspended in130 parts of o- Parts of 4 (2 hydrOXy 'naphthoyn-ammo' dichlorobenzene,heated to 120 to 125 C. and mixed 2,5-diphenyl-l,3,4-triazole aredissolved cold in a mixture of 150 parts of ethanol, 50 parts of waterand 3.0 $3 gi fi g gifi is r i K3 2228312: parts of 30 percent sodiumhydroxide solution. 1 Part of the condensation product of 8 mols ofethylene oxide and 1 mol of p-tert.-octylphenol is added to the solutionand the naphthol is subsequently precipitated by means of acetic acidwith good stirring. The product is coupled by adding the diazo solutiondescribed in paragraph 1 maintaining a pH value of 6.0 to 6.5 and atemperature of 15 to 20 C. To complete the coupling, the mixture isstirred for a further hour at the same 1.51 Parts of anthranilic acidmethyl ester are diazotized with aqueous hydrochloric acid, ice andsodium nitrite in the customary manner.

decomposition of the diazo-amino compound and the coupling to form thepigment are completed. The red pigment is filtered hot, and rinsed withhot 0- dichlorobenzene, cold methanol and hot water. After drying invacuo at 80 C., 2.1 parts of an orange monoazo dyestuff of the formulatemperature and then stirred for another hour at to (31% C. Theresulting pigment suspension is rendered S5 acid to Congo Red by addinghydrochloric acid and fil- O tered. The product is washed with hot wateruntil 0H OZOQHS chloride ions can no longer be detected in the filtrate.N---N After drying at 80 to C in vacuo, the orange pig- OJl LGCH, mentdyestuff of the formula 60 5 are obtained in a soft form. The dyestuffis sparingly NN soluble to insoluble in the customary solvents and dyesC l LO polyvinyl chloride film and lacquers orange shades having goodfastness to migration, overstripe bleeding and H light.

EXAMPLE 7 wherein X denotes hydrogen, chloro, bromo or lower alkyl, Xand X each denotes hydrogen, chloro, bromo, lower alkyl, lower alkoxy,phenoxy, nitro, cyano, carboxylic acid lower alkyl or phenyl ester,lower alkylsulphonyl, phenyl lower alkyl sulphonyl, trifluoromethyl,sulphonic acid phenyl amide, sulphonic acid lower alkyl or phenyl ester,or a group of the formula -CONHR-, in which R denotes hydrogen, loweralkyl, unsubstituted phenyl or phenyl substituted by chloro, loweralkyl, lower alkoxy, trifluoromethyl or lower carbalkoxy groups, Xdenotes hydrogen, bromo, lower alkoxy, nitro or cyano, Y, and Y eachdenotes hydrogen, chloro or lower alkyl, Z and Z each denoted hydrogen,chloro, lower alkyl, lower alkoxy, trifluoromethyl or lower carbalkoxy,and R denotes lower alkyl, phenyl or hydrogen.

2. An azo pi'gment as claimed in claim 1 of the formula 3. The compoundas claimed in claim 1 of the formula 5. The compound as claimed in claim1 of the formula mm OH 01 NN 4mll L G 6. The compound as claimed inclaim 1 of the formula 7. The compound as claimed in claim 1 of theformula Cl I 8. The compound as claimed in claim 1 of the formula

2. An azo pigment as claimed in claim 1 of the formula
 3. The compoundas claimed in claim 1 of the formula
 4. The compound as claimed in claim1 of the formula
 5. The compound as claimed in claim 1 of the formula 6.The compound as claimed in claim 1 of the formula
 7. The compound asclaimed in claim 1 of the formula
 8. The compound as claimed in claim 1of the formula